A series of new functional poly(ethylene-co-vinyl alcohol)-g-polystyrene graft copolymers (EVAL-g-PS) with controlled molecular weight (M_n = 38,000–94,000 g mol⁻¹) and molecular weight distribution (M_w/M_n = 2.31–3.49) were synthesized via a grafting from methodology. The molecular structure and component of EVAL-g-PS graft copolymers were confirmed by the analysis of their ¹H NMR spectra and GPC curves. The porous films of such copolymers were fabricated via a static breath-figure (BF) process. The influencing factors on the morphology of such porous films, such as solvent, temperature, polymer concentration, and molecular weight of polymer were investigated. Ordered porous film and better regularity was fabricated through a static BF process using EVAL-g-PS solution in CHCl₃. Scanning electron microscopy observation reveals that the EVAL-g-PS graft copolymer is an efficient compatibilizer for the blend system of low-density polyethylene/polystyrene. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 516–524

New block copolymers Polystyrene-b-poly (2,2,2-trifluoroethyl acrylate)-b-Polystyrene (PS-PTFEA-PS) with controlled molecular weight (M_n=5000-11000 g⋅mol⁻¹) and narrow molecular weight distribution (M_w/M_n=1.13-1.17) were synthesized via RAFT polymerization. The molecular structure and component of PS-PTFEA-PS block copolymers were characterized through ¹H NMR, ¹⁹F NMR, GPC, FT-IR and elemental analysis. The porous films of such copolymers with average pore size of 0.80-1.34 μm and good regularity were fabricated via a static breath-figure (BF) process. The effects of solvent, temperature, and polymer concentration on the surface morphology of such film were investigated. In addition, microstructured spheres and fibers of such block copolymers were fabricated by electrospinning process and observed by scanning electron microscopy (SEM). Furthermore, the hydrophobicity of porous films, spheres, and fibers was investigated. The porous film showed a good hydrophobicity with the water-droplet contact angles of 129°, and the fibers showed higher hydrophobicity with the water-droplet contact angles of 142°. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 678–685

A series of well-defined three-arm star poly(ε-caprolactone)-b-poly(acrylic acid) copolymers having different block lengths were synthesized via the combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). First, three-arm star poly(ε-caprolactone) (PCL) (M_n = 2490–7830 g mol⁻¹; M_w/M_n = 1.19–1.24) were synthesized via ROP of ε-caprolactone (ε-CL) using tris(2-hydroxyethyl)cynuric acid as three-arm initiator and stannous octoate (Sn(Oct)₂) as a catalyst. Subsequently, the three-arm macroinitiator transformed from such PCL in high conversion initiated ATRPs of tert-butyl acrylate (^tBuA) to construct three-arm star PCL-b-P^tBuA copolymers (M_n = 10,900–19,570 g mol⁻¹; M_w/M_n = 1.14–1.23). Finally, the three-arm star PCL-b-PAA copolymer was obtained via the hydrolysis of the PtBuA segment in three-arm star PCL-b-P^tBuA copolymers. The chain structures of all the polymers were characterized by gel permeation chromatography, proton nuclear magnetic resonance (¹H NMR), and Fourier transform infrared spectroscopy. The aggregates of three-arm star PCL-b-PAA copolymer were studied by the determination of critical micelles concentration and transmission electron microscope. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Well-defined polymethylene-block-polystyrene (PM-b-PS) diblock copolymers were synthesized via a combination of polyhomologation of ylides and reversible addition-fragmentation chain-transfer (RAFT) polymerization of styrene. Trithiocarbonate-terminated polymethylenes (PM-TTCB) (M_n = 1400 g mol⁻¹; M_w/M_n = 1.09 and M_n = 2100 g mol⁻¹; M_w/M_n = 1.20) were obtained via an esterification of S−1-dodecyl-S′-(α,α′-dimethyl-α″-acetate) trithiocarbonate with hydroxyl-terminated polymethylene synthesized via polyhomologation of ylides followed by oxidation. Then, a series of PM-b-PS (M_n = 5500–34,000 g mol⁻¹; M_w/M_n = 1.12–1.25) diblock copolymers were obtained by RAFT polymerization of styrene using PM-TTCB as a macromolecular chain-transfer agent. The chain structures of all the polymers were characterized by proton nuclear magnetic resonance (¹H NMR), gel permeation chromatography, and Fourier transform infrared spectroscopy. The thiocarbonylthio end-group of PM-b-PS was transformed into thiol group by aminolysis and confirmed by UV–vis spectroscopy. In addition, microfibers and microspheres of such diblock copolymers were fabricated by electrospinning process and observed by scanning electron microscopy (SEM). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2892–2899

Well-defined amphiphilic polymethylene-b-poly(ε-caprolactone)-b-poly(acrylic acid) (PM-b-PCL-b-PAA) triblock copolymers were synthesized via a combination of polyhomologation, ring-opening polymerization (ROP), and atom transfer radical polymerization (ATRP). First, hydroxyl-terminated polymethylenes (PM-OH; M_n = 1100 g mol⁻¹; M_w/M_n = 1.09) were produced by polyhomologation followed by oxidation. Then, the PM-b-PCL (M_n = 10,000 g mol⁻¹; M_w/M_n = 1.27) diblock copolymers were synthesized via ROP of ε-caprolactone using PM-OH as macroinitiator and stannous octanoate (Sn(Oct)₂) as a catalyst. Subsequently, the macroinitiator transformed from PM-b-PCL in high conversion initiated ATRPs of tert-butyl acrylate (^tBA) to construct PM-b-PCL-b-P^tBA triblock copolymers (M_n = 11,000–14,000 g mol⁻¹; M_w/M_n = 1.24–1.26). Finally, the PM-b-PCL-b-PAA triblock copolymers were obtained via the hydrolysis of the P^tBA segment in PM-b-PCL-b-P^tBA triblock copolymers. The chain structures of all the polymers were characterized by gel permeation chromatography, proton nuclear magnetic resonance, and Fourier transform infrared spectroscopy. Porous films of such triblock copolymers were fabricated by static breath-figure method and observed by scanning electron microscope. The aggregates of PM-b-PCL-b-PAA triblock copolymer were studied by transmission electron microscope. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Well-defined amphiphilic polymethylene-b-poly (acrylicacid) diblock copolymers have been synthesized via a new strategy combining polyhomologation and atom transfer radical polymerization (ATRP). Hydroxyl-terminated polymethylenes (PM-OH) with different molecular weights and narrow molecular weight distribution are obtained through the polyhomologation of dimethylsulfoxonium methylides following quantitative oxidation via trimethylamine-N-oxide dihydrate. Subsequently, polymethylene-based macroinitiators (PM-MIs M_n = 1,300 g mol⁻¹ [M_w/M_n = 1.11] and M_n = 3,300 g mol⁻¹ [M_w/M_n = 1.04]) are synthesized by transformation of terminal hydroxyl group of PM-OH to α-haloester in ∼100% conversion. ATRPs of tert-butyl acrylate (t-BuA) are then carried out using PM-MIs as initiator to construct PM-b-P(t-BuA) diblock copolymers with controllable molecular weight (M_n = 8,800–15,800 g mol⁻¹ M_w/M_n = 1.04–1.09) and different weight ratio of PM/P(t-BuA) segment (1:1.7–1:11.2). The amphiphilic PM-b-PAA diblock copolymers are finally prepared by hydrolysis of PM-b-P(t-BuA) copolymers and their self-assembly behavior in water is preliminarily investigated via the determination of critical micelle concentrations, dynamic light scattering, and transmission electron microscope (TEM). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012